Effects of cobalt metal addition on sintering and ionic conductivity of Sm(Y)-doped ceria solid electrolyte for SOFC

The effects of cobalt addition (0.5 and 1 wt.%) on densification and ionic conductivity of Ce_0.9Sm_0.1O_1.95 (10SDC) and Ce_0.9Sm_0.075Y_0.025O_1.95 (2.5Y-SDC) have been studied. X-ray diffraction (XRD) showed that Co had changed to Co₃O₄ and Co₃O₄ + CoO after firing at 900 °C and 1300 °C respectively. The addition of Co promoted densification to occur at lower temperatures with a more uniform grain growth and greatly improved both grain boundary and bulk conductivity for 10SDC. Significant improvement of grain boundary for the 2.5Y-SDC samples was obtained, even at 1300 °C sintering, while bulk conductivity was slightly improved. Rapid grain growth along with improvement of ionic conductivity was observed when the samples were sintered further at higher temperature. Superior ionic conductivity of the 2.5Y-SDC samples with Co addition to that of the bare 10SDC suggested the potential use of Co as the co-dopant in this system to reduce the content of costly rare earth usage.     

The role of electrolyte in governing the performance of protonic solid state battery

The solid-state proton conductor, P₂O₅.5H₂O, is found very difficult to handle due to presence of a very high content of moisture and corrosive nature. The addition of Al₂O₃ and SiO₂ into P₂O₅.5H₂O, forming composite electrolytes, obviates said drawback. The Zn + ZnSO₄ used as an anode to prepare cells with different cathode viz. I₂, MnO₂, PbO₂, and V₆O₁₃ characterized under different conditions. Open circuit voltage, discharge current and discharge time, on load voltage, discharge capacity, power density, and energy density are evaluated from discharge properties. Protonically conducting composite 70(P₂O₅.5H₂O)/30[(92SiO₂)/08(Al₂O₃)] is found to be the optimum combination with the optimized 50Zn/50ZnSO₄ as anode and 40MnO₂/60 graphite as cathode from secondary battery view point. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Characterization of solid electrolytes prepared from ionic glass and ionic liquid for all-solid-state lithium batteries

Glassy solid electrolytes were prepared by combining the 50Li₂SO₄·50Li₃BO₃ (mol%) ionic glass and the 1-ethyl-3-methyl-imidazolium tetrafluoroborate ([EMI]BF₄) ionic liquid. High-energy ball milling was carried out for the mixture of the inorganic ionic glass and the organic ionic liquid. The ambient temperature conductivity of the glass electrolyte with 10 mol% [EMI]BF₄ was 10⁻⁴ S cm⁻¹, which was three orders of magnitude higher than that of the 50Li₂SO₄·50Li₃BO₃ glass. The addition of [EMI]BF₄ to the ionic glass decreased glass transition temperature (T_g) of the glass and the decrease of T_g is closely related to the enhancement of conductivity of the glass. Morphology and local structure of the glass electrolyte was characterized. The dissolution of an ionic liquid in an ionic glass with Li⁺ ion conductivity is a novel way to developing glass electrolytes for all-solid-state lithium secondary batteries.     

Effect of fillers on magnesium–poly(ethylene oxide) solid polymer electrolyte

A solid polymer electrolyte (SPE) film consisting of poly(ethylene oxide) (PEO) with magnesium chloride as electrolytic salt and B₂O₃ as the filler has been prepared by solution casting technique. The polymeric film was flexible and self-standing with proper mechanical strength and studied for application in a solid-state rechargeable magnesium battery. The interactions between the filler and PEO chains are studied by differential scanning calorimeter and Fourier transform infrared techniques. Composition of SPE is optimized, and maximum conductivity is obtained at 2 wt% B₂O₃. Filler seems to increase the number of free magnesium cations by decoordinating the bond between magnesium cations and ether oxygen of PEO. Cyclic voltammetry results show the reversible capability of magnesium electrode. Solid-state magnesium cell employing magnesium anode, SPE, and manganese oxide was assembled, and its open circuit voltage is found to be 1.9 V.     

Computational screening of lactam molecules as solid electrolyte interphase forming additives in lithium-ion batteries

N-Substituted acetyl ε-caprolactam is known as a novel solid electrolyte interphase (SEI)-forming additive for improving the cycle performance of LiCoO₂/graphite lithium-ion batteries. We suggest four lactam derivatives as promising candidates for SEI-forming additives with a higher performance than N-acetyl ε-caprolactam as determined via first-principles density functional calculations of oxidation potentials, reduction potentials, and Li⁺ binding affinities. This computational screening protocol provides a shortcut for development of new SEI-forming electrolyte additives in lithium-ion batteries.     

Properties of doped ceria solid electrolytes in reducing atmospheres

In this work we present investigations of stability of rare earth-doped ceria electrolytes in reducing atmosphere. The effect of dopant type and dopant concentration on reducibility was studied on the basis of thermogravimetric and impedance spectroscopy measurements on materials grouped into two series: Ce_1 − xGd_xO_2 − x/2 (0 ≤ x ≤ 0.4) and Ce_0.85R_0.15O_1.925 (R = Y, Nd, Sm, Gd, and Dy). Relationship between an initial vacancy concentration introduced by the amount of dopant and the characteristic temperature of reduction was found. Much less pronounced dependence was observed for different dopants with the same concentration, which indicates that it is the dopant and vacancy concentration and not the dopant type, which is responsible for reducibility of ceria electrolytes. Impedance spectroscopy measurements allowed for calculation of changes of oxygen ions transport number during the reduction process.     

Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes

Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La_9.333 + xSi₆O_26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La₁₀Si₆O₂₇ on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mⁿ⁺) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La₁₀(Si_5.8Al_0.2)O_26.9}-α(FeO_γ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10^− 3 and 2.9 × 10^− 3 under P(O₂) = 1.1 × 10⁴ Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La₁₀(Si_5.8Al_0.2)O_26.9}-0.005(FeO_γ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.     

Effects of novel benzotriazole based zwitterionic salt as electrolyte additive for lithium ion batteries

A novel zwitterionic lithium-benzotriazole sulfobetaine is fabricated by grafting 1,3– propanesultone onto benzotriazole and then lithiating it. The resultant lithium-benzotriazole-sulfobetaine additive is used as an electrolyte additive in lithium ion batteries in 1 M LiPF₆ (ethylene carbonate/dimethyl carbonate = 1:1). The electrolytes with the lithium-benzotriazole sulfobetaine shows higher ionic conductivities (2.18 $\times$ 10⁻² S cm⁻¹) compared to the bare electrolyte (1.07 $\times$ 10⁻² S cm⁻¹) and greater electrochemical stability (anodic limit at ~5.5 V vs. Li/Li⁺) than the pure electrolyte (anodic limit at ~4.6 V vs. Li/Li⁺). The discharge capacity of the lithium cobalt oxide/graphite cells is improved at higher C-rates with the addition of lithium-benzotriazole sulfobetaine due to increased ionic conductivity. The lithium cobalt oxide/graphite cells with the lithium-benzotriazole sulfobetaine additive also show stable cycling performance. These findings warrant the use of lithium-benzotriazole sulfobetaine as an electrolyte additive in lithium ion batteries.     

Electrochemical conversion of carbon dioxide in a solid oxide electrolysis cell

Carbon dioxide is one of the greatest concerns worldwide, since it is not only a major greenhouse gas but also expected to be an important, sustainable resource for fuels and chemicals. The electrochemical conversion of carbon dioxide, based on solid electrolyte membrane reactors, has the promise to overcome the limitations of the conventional catalytic reactors such as the limited conversion and kinetics, relatively low selectivity and high energy consumption. In this review, electrocatalysts and solid oxide electrolytes, both proton and oxide ion conductors as core materials in an electrochemical ceramic membrane reactor have been reviewed and particular emphasis is placed on their application to synthesize carbon monoxide and hydrogen.     

Surface energies of metals in both liquid and solid states

Although during the last years one has seen a number of systematic studies of the surface energies of metals, the aim and the scientific meaning of this research is to establish a simple and a straightforward theoretical model to calculate accurately the mechanical and the thermodynamic properties of metal surfaces due to their important application in materials processes and in the understanding of a wide range of surface phenomena. Through extensive theoretical calculations of the surface tension of most of the liquid metals, we found that the fraction of broken bonds in liquid metals (f) is constant which is equal to 0.287. Using our estimated f value, the surface tension (γ_m), surface energy (γ_SV), surface excess entropy (−dγ/dT), surface excess enthalpy (H_s), coefficient of thermal expansion (α_m and α_b), sound velocity (c_m) and its temperature coefficient (−dc/dT) have been calculated for more than sixty metals. The results of the calculated quantities agree well with available experimental data.     

Scaling predictions for thermodynamical properties of finite-size liquid systems

The notion of spatial limitation of a system undergoing critical phenomena and phase transitions is presented. The scaling formulae for the singular part of the fluctuation free energy and correlation length for spatially limited liquid systems are analyzed. The conducted research supports the conclusion that reducing of the volume's size leads, after the decreasing of the correlation length, to decreasing of the susceptibility χ, which is equivalent to isothermal compressibility β_T for one-component liquid.     

EAST 装置离子回旋加热液态阻抗匹配系统的研究

介绍了EAST 装置离子回旋加热系统中的两种实现阻抗匹配的方式, 用三支节液态调配器取代传统的滑竿式三支节调配器和用液态相移器与单支节液态调配器相结合组成液态阻抗匹配系统。通过对液态阻抗匹配系统的分析, 表明这两种方式都能够较好地实现阻抗匹配。     

超导重力仪用液氦恒温器研制

介绍了一套超导重力仪用液氦恒温器,包括技术指标要求、总体结构、关键技术、试验步骤及结果.恒温器液氦消耗量为0.8L/h,真空腔体内部温度稳定度为±5mK,低温下真空腔体真空度优于5×10-4pa,各参数均优于技术指标要求,完全满足超导重力仪工作环境要求.表明该设计方案是合理的,试验流程是正确的.     

用于测量流量和含沙量的超声波液位测定系统

本文介绍了实验室内用于测量流量和含沙量的超声波液位测定系统，此系统采用气介式方案，选用复合材料高频换能器作为超声波发射／接收器件，结构简单，静态测量时测量误差在１５０ｍｍ范围内不超过１ｍｍ，并可与微机进行远距离通讯。     

螺旋型波纹管流阻测量系统研制及液氮压降测量

超导电缆芯通常内嵌于真空绝热波纹管并被管内低温流动介质冷却和保护。螺旋型波纹管因一次成型制作长度上的优势更适合于大长度超导电缆应用。设计并搭建了螺旋型波纹管液氮流动压降特性实验台,不仅可以方便地更换被测波纹管样品,而且允许插入不同规格的线芯模拟物。利用该实验台测量了液氮流量1～9 L/min区间内不同规格(通径11～15 mm)螺旋型波纹管插入4 mm线芯后的流动压降特性。实验结果验证了三维波纹管压降损失数值模型的准确性。同时,通过进行不同尺寸波纹管实验,发现尺寸变化对摩擦因子变化规律的影响不明显,这为通过该实验台获得小管径实验数据用于指导大管径实际应用波纹管设计提供了理论基础。     

A proposed method for generating and receiving narrow beams of ultrasound in the Fast Reactor liquid sodium environment

In the liquid sodium coolant of the Fast Reactor there are several measurements which may be performed using ultrasonic techniques. This paper gives a brief outline of one such measurement and then describes the design of an ultrasonic waveguide for the generation and detection of ultrasound in this hostile situation. The successful laboratory tests of the device are also reported.     

Effect of La3+ and Pr3+ co-doping on structural,thermal and electrical properties of ceria ceramics as solid electrolytes for IT-SOFC applications

In the present investigation, the effect of La³⁺ and Pr³⁺ co-doping on structural, thermal and electrical properties of ceria ceramics useful as solid electrolytes in intermediate temperature solid oxide fuel cells (IT-SOFCs) has been studied. The co-doped ceria Ce_0.8Pr_0.2–xLa_xO_2-δ samples have been prepared successfully via sol-gel auto-combustion synthesis. The high dense ceramic samples have been achieved by carry out an optimized conventional sintering at 1300 °C for 4 h. The powder X-ray diffraction analysis of all the co-doped ceria ceramics revealed the single phase with cubic-fluorite structure formation. Crystallographic information has been carried out from the powder X-ray diffraction and Rietveld refinement analysis. The scanning electron microscope and energy dispersive spectroscopy analysis revealed the smaller grain size with high density in microstructure and stoichiometric elemental confirmations. Raman spectra of prepared ceramics revealed the information of phase and oxygen vacancy formation in the entire compositions. The dilatometric studies of prepared co-doped ceria ceramics revealed the moderate coefficients of thermal expansion. The electrical parameters such as total conductivities and activation energies have been studied with the help of impedance spectroscopy. Among all these co-doped ceria ceramic samples, Ce_0.80Pr_0.10La_0.10O_2−δ found to exhibit the highest value of total ionic conductivity with minimum activation energy and this makes it could be a promising electrolyte material for IT-SOFC applications.     

Physicochemical properties of NaxCoO2 as a cathode for solid state sodium battery

An intercalation compound with composition Na_0.7CoO₂ has been synthesized through different preparative techniques such as solid state reaction, ball milling and sol gel techniques. The investigation reveals that the cathode material with an average particle size of about 500 nm of uniform morphology can be synthesized through sol gel technique. Further, this synthesis technique improves the stoichiometry of the sodium content significantly. The electrical resistivity of these cathode materials is found to be in the range of 4 to 12 mΩ-cm at 300 K. It has been observed that, the resistivity of the cathode material increases with increase in sodium content. The electrochemical cells with the configuration Na | [wt.% 0.3 PEO-0.7 PEG]₆:NaPO₃ |composite cathode material, have shown an open circuit voltage (OCV) value of 2.7 V. The (OCV) of the cells with the cathode prepared by sol-gel and ball milling route has shown a plateau region of about 40 h, when compared to the plateau region of 10 h for the battery with the cathode prepared by solid state reaction. The reduction in the particle size of the cathode material has improved the stability of the electrode electrolyte interface and thereby discharges characteristics.     

Structural and electrical properties of pure and NaBr doped poly (vinyl alcohol) (PVA) polymer electrolyte films for solid state battery applications

A sodium ion conducting polymer electrolyte based on poly (vinyl alcohol) (PVA) complexed with sodium bromide (NaBr) was prepared using solution cast technique. Several experimental techniques such as XRD, FTIR, SEM, temperature-dependant conductivity and transference number measurements have been performed. XRD and FTIR studies confirm the complexation of salt with the polymer. Surface morphology was studied using Scanning Electron Microscopy. DC conductivity was measured in the temperature range of 303–373 K, and the conductivity was found to increase with the increase of dopant concentration as well as temperature. Transference number data suggests that the charge transport in this polymer electrolyte system is mainly due to ions. Using these polymer electrolyte films, electrochemical cells were fabricated with configuration Na/(PVA:NaBr)/V₂O₅ and Na/(PVA:NaBr)/(I2+C+electrolyte) and their discharge characteristics like open circuit voltage (OCV), short circuit current (SCC), power density, energy density were evaluated and compared. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Development of vulcanizable elastomers suitable for use in contact with liquid oxygen

For the past few years our research has been concerned with the preparation of polymers which are compatible with and have usable mechanical properties in the presence of liquid oxygen. These are stringent requirements and the need for oxidative stability necessitated investigation of halogen-containing polymers, in particular, polymers containing fluorine. Since only a few fluorocarbon monomers are commercially available, this study required an extensive synthesis program. A comprehensive search of the literature and an attempt to systematically study the effect of polymer structure on low-temperature properties directed our initial work toward the synthesis of some novel, highly fluorinated vinyl monomers and polymers. In this article the effect of structure on polymer glass transition temperatures will be discussed and the synthesis and characterization of some fluorocarbon vinyl ethers and their polymers will be described.